JPH02272444A - silver halide photographic materials - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (A) Industrial Application Field The present invention relates to a silver halide photographic material spectrally sensitized to red light, and more particularly to printing using a helium-neon laser as a light source. This invention relates to a silver halide photographic light-sensitive material for plate making.

(B) Prior art and problems In recent years, with the rapid development of optoelectronics technology, light sources such as laser light and LED light have replaced conventional incandescent light bulbs as light sources used for image processing by converting signal current into electricity. is used.

Under these circumstances, a high-output argon laser has been used as a light source for dot generator type scanners, but this light source has the drawbacks that the entire device is bulky and expensive, and the life of the light source is short. Therefore, recently, helium-neon lasers have attracted attention as a light source to replace argon lasers and have been put into practical use. but,
This light source has a low output and is required to be highly sensitive to photosensitive materials.

JP-A-62-58240, JP-A-62-62354, JP-A-62-62355, and JP-A-63-109436 propose the combination of at least two types of sensitizing dyes for supersensitization to red light. has been done.

In recent years, the demand for rapid processing has increased, and it is well known that silver halide emulsions containing silver chloride as a main component are used for this purpose.

However, even if a silver halide emulsion containing silver chloride is subjected to supersensitization as described in the above patent, it cannot be said that sufficiently high sensitivity to helium-neon laser light can be obtained.
Furthermore, there is a demand for silver halide photographic materials that have higher sensitivity and are free from residual color of sensitizing dyes even during rapid processing.

(C) Purpose of the Invention The purpose of the present invention is to provide a silver halide photographic material with high sensitivity and good dye removal for an output device using a helium-neon laser as a light source.

(D) Structure of the Invention The above object of the present invention is that the silver halide grains are silver chlorobromide or silver chloroiodobromide containing 50 moles or more of silver chloride, and the following (a) and (b) This was achieved using a silver halide photographic material that satisfies the conditions (C) and (C).

(a) In the silver halide grains contained in the above-mentioned silver halide photographic material, the molar ratio is 0.1 to 1. (An emulsion in which chlorine and bromide ions on the grain surface portion in an amount corresponding to 1 are replaced by iodide ions.

(b) The silver halide emulsion has the following general formula [■], (
A silver halide emulsion supersensitized with at least 2s of the sensitizing dyes represented by II) and [■].

General formula [■] [-Formula [I], R1 is an unsubstituted or substituted alkyl group (for example, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a pentyl group, or a substituted alkyl group) are β-hydroxyethyl group, T-hydroxyethyl group, β-acetoxy 1-/L4.β-benzoyloxyethyl group, γ-acetoxypropyl group, β-methoxyethyl group.

r-methoxypropyl group, carboxymethyl group, β-carboxyethyl group, γ-carboxypropyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group,
β-methoxycarbonylethyl group, γ-methoxycarbonylpropyl group, β-sulfoethyl group, γ-sulfopropyl group, γ-sulfobuty/L/ group, -sulfobutyl group, allyl group, benzyl group, phenethyl group, P-sulfobenzyl group (base, etc.).

When the dye is of the sulfo anion type, 1 of the sulfonic acid
One is alkali metal salts (e.g., potassium salts, sodium salts, etc.) and ammonium salts (e.g., ammonium!,
) ethyl ammonium salt, pyridinium salt, etc.) can be obtained.

R2 represents a sulfoalkyl group (eg, β-sulfoethyl group, γ-sulfopropyl group, γ-sulfobutyl group, -sulfobdel group, etc.) or a sulfoaralkyl group (eg, sulfobenzyl group, sulfophenethyl group, etc.). R3 represents a lower alkyl group such as a methyl group, ether group, or butyl group, and w, , w2 each represent an alkylene group (eg, methylene group, ethylene group, propylene group, etc.). ]General numeral ID [-In formula [11], Ws-W4 is an alkyl group (
For example, it represents a numerical formula [a lower alkyl group as described for R1 in ID], an alkoxy group (eg, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), a hydroxy group. R4 represents an alkyl group as described for R11 in the general formula [ID, and R5 represents a sulfoalkyl group or a sulfoaralkyl group as described for R2 in the general formula m. R6 represents a lower alkyl group such as a methyl group, an ethyl group or a butyl group. ] General number total 1 [[] [-In the formula (II [), R7 is an alkyl group as described for R1 in the general formula [ID], Ra is R2 in the general formula [11]
represents a sulfoalkyl group or a sulfoaralkyl group as described above. Ri9 represents a lower alkyl group such as a methyl group, ethyl group, butyl group. Wy, We are general formulas [
W3 to W6 in 1) represent an alkyl group, an alkoxy group, or a hydroxy group. (e) A silver halide emulsion containing at least one of a mercaptotetrazole and a tetrazaindene compound in an amount of 10-4 to 10-2 mol per mol of silver halide.

This will be explained more specifically.

The iodine substitution on the surface of the silver halide grains in (a) can be carried out at any time, but it is generally preferable to carry it out after the completion of physical ripening and before addition of the sensitizing dye.

The iodine substitution is in an amount of 0.1 to 1 mole, preferably 0.1 to 0.6 mole, based on the silver halide grains.

The iodine-substituted silver halide emulsion further enhances the supersensitizing effect of the sensitizing dye, and generally has a molecular weight of 600 to 65
It shows maximum sensitivity at 0 nm and 650-700 nm, but
Along with the strong color feeling, a problem arises in that the residual color of the dye increases after the development process.

This problem is solved by adding 10% of the mercaptotetrazole or tetrazaindene compound (C) per mole of silver halide.
It has been found that by adding 5 to 10 mol of the dye, the residual color property of the dye can be improved without substantially reducing the sensitivity at 633 nm, which is the output wavelength of helium-neon laser light.

Next, specific examples of the sensitizing dyes represented by the above-mentioned formulas [ID, [■] and [■] will be listed, but the sensitizing dyes used in the present invention are not limited thereto.

Specific examples of sensitizing dyes indicated by Ichimon hole CI, l [:
I-A] I-BE [:I-D:] CI-E) [1-F] 5(J!M [:Ir-C) [:ff-D) 1:[-E] Us U3 (1 -G) Specific examples of sensitizing dyes represented by general formula [n) [I[
-A] [:II-B] Station OsH Sauce Os [:I[-F] Specific example C of the sensitizing dye represented by general formula (III)
III-A) [III-B, 1 General formula CI used in the present invention), [■] and [■]
The sensitizing dye represented by can be synthesized by a known method.

For example, U.S. Patent Nos. 2,503,776 and 3.1
17.210, British Patent No. 742,112, German Patent No. 929,080, and German Patent No. 1,072,765, those skilled in the art can easily synthesize the compound.

The silver halide photographic emulsion used in the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. produced by a conventional method, and the sensitizing dye can be added to these silver halide emulsions as a solution in a solvent such as methanol, isopropanol, pyridine, dimethylformamide, water, etc. alone or in combination. It can also be added to the emulsion using ultrasonic dispersion. Furthermore, U.S. Patent Nos. 3,482,981, 3,585,195, and 3,469,987
No. 3,649,286, No. 3,485,63
No. 4, No. 3,342,605 and No. 2,912
．． The method described in No. 343 can also be used.

The amount added varies depending on the type of sensitizing dye or the type of silver halide photographic emulsion, but it is usually calculated as IKf in terms of silver nitrate.
In contrast, the total amount of the compounds of formulas [1], [■] and [■] can be used in a wide range of 0.01f to 10F, and the mixing ratio in that case is 1:0.1 to 10. :0.
Although the range of 1 to 10 (molar ratio) is preferable, it may be outside this range if necessary.

They may be added to the emulsion separately or as a mixed solution.

The silver halide photographic emulsions used in the present invention include noble metal sensitization, sulfur sensitization, reduction sensitization, and combinations thereof.
Alternatively, a polyalkylene oxide compound or the like may be added.

The silver halide photographic emulsion of the present invention may be spectrally sensitized using other sensitizing dyes, such as cyanine and merocyanine, as required, and may further be sensitized using known methods such as stabilizers, development inhibitors, capri Additives such as inhibitors, surfactants, hardeners may be included.

Examples of the mercaptotetrazole compound used in the present invention include compounds represented by the general formula [■].

General formula [1 In the formula, Y represents an aromatic group or a 5- or 6-membered heterocyclic group.

The aromatic group represented by Y is preferably an aryl group, such as a phenyl group or a naphthyl group. The heterocyclic group represented by Y is preferably a nitrogen-containing heterocyclic group, such as 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group,
6-quinolyl group, 2-thienyl group, 3-furyl group, 3-
Examples include pyrrolyl group, 2-imidazolyl group, 2-pyrimidinyl group, 3-pyridazinyl group, 3-isoquinolyl group, and 2-thiazolyl group.

These aromatic groups and heterocyclic groups may have substituents, specifically halogen atoms (for example, chlorine, bromine, iodine, etc. atoms), hydroxyl groups, amino groups, cyano groups,
Nitro groups, carboxyl groups and their salts, sulfo groups and their salts, alkyl groups (e.g. methyl, ethyl, 5e
%2 of c-pentyl, octyl, etc.! s), alkoxy groups (e.g. 6 groups such as methoxy, nidoxy, 2-ethylhexyloxy), aryl groups (e.g. phenyl group, naphthyl group, etc.), aryloxy groups (e.g. phenoxy group,
phenethyloxy group, etc.).

Further, as the tetrazaindene compounds used in the present invention, there are those represented by the following general formulas (V) to (■).

General formula (V) - Mathematical formula (W) - Mathematical formula (■)
- Formula (■) (in the formula, 几1o, Rtt
and R12 may be the same or different and each represents a hydrogen atom, a halogen atom, an amino group, a derivative of an amino group, an alkyl group, a derivative of an alkyl group, an aryl group or a derivative of an aryl group. ) Examples of mercaptotetrazole compounds and tetrazaindene compounds are shown below, but are not limited to these.

Examples of Mercaptotetrazole Compounds Examples of Tetrazaindene Compounds These mercaptotetrazole or/and tetrazaindene compounds contain 10-
4 to 10-2 moles, preferably 2X10'' to 5X10
-s mol is added. Although the timing of addition is arbitrary, it is preferably added after the sensitizing dye is added.

The silver halide emulsion used in the present invention contains silver chloride bromide containing at least 50 moles, preferably 60 moles of silver chloride,
It consists of an emulsion of silver chloroiodobromide, and its grain surface is 0.1 to 1
It was converted with morti iodide.

It is desirable that the silver halide grains used in the present invention be monodisperse, and the degree of monodispersity can be defined by the following formula.

For convenience, the grain size of the silver halide grains according to the present invention is expressed as the diameter of a cubic crystal grain, or in the case of non-cubic crystal grains, the projected area is converted into a circle, and the average value is expressed as the average grain size (7). do. The degree of monodispersity is expressed as a value obtained by dividing the standard deviation of particle diameter by the average particle diameter (7) and multiplying it by 100.

Here, if we express the degree of monodispersity in the formula, becomes.

In the present invention, it is important to prepare the /S silver halide grains so that this value is 20 or less; if the monodispersity exceeds 20, high contrast will be impaired and sharpness will deteriorate, which is undesirable. .

Furthermore, the silver halide grains to be used may be used for a while, or two or more rings having different average grain sizes may be blended at any time after grain formation to obtain a predetermined gradation. You may also serve it. It can also be used in combination with various other silver halide grains.

When carrying out the invention, the photographic emulsion of the invention may be used, for example, as described by Glafkides, P.
Chiemi Kou Photography (Chi
mie et Physique Photograp
hique: Published by Pau1Monte1) 1967
2013, C.F. Duffi
n), ``Photography')ri@f-2 Lujiron Chemistry'' published by The 7Ocal Press (Photog
rapic emulsion chemistry
: The Focal Press) 1966,
Bui El Zelikman, et al. (V, L, Zel i
"Making and Coating Photographic Emulsion 1" by KMAN, AT, AL, )
Published by The 7 Orcal Press (Mak-ing and
Coating Photographic Emul
sion: published by The Focal Press) 19
It can be prepared using the method described in 1964 et al. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided synthesis method, a simultaneous mixing method, or a combination thereof.

A method in which particles are formed in an excess of silver ions (so-called back-mixing method) can be used.

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Silver halide emulsions having two or more rings formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, it can be made to coexist with a compound containing a metal belonging to Group 8.

These compounds are preferably added in an aqueous solution during or after grain formation, physical or chemical ripening of the silver halide emulsion, and are added in an amount of about 10-9 per mole of silver halide.
It is sufficient to add ~10-5 moles, but if desensitization or reversal is likely to occur depending on the type of metal in the compound used, emulsion preparation method, development method, etc., add 10 to 10 moles per mole of halogenation. It is preferable to use it before the completion of ripening.

In order to remove soluble salts from the emulsion after precipitation or physical ripening, the Tardel water washing method, which involves gelatin gelation, may be used. A precipitation method (flokynylation method) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may also be used.

The silver halide emulsion may be used after being chemically sensitized as usual. For chemical sensitization, for example, H. Fr1eser (ed.), "D. Grundlage
n der Photography Pro
zesse mit Sllberhalogenid
en: (Akad-emische Verala
gs Ge5ellschaft) 1968°67
The method described on pages 5 to 734 can be used.

As a binder for silver halide emulsions, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single or copolymers may also be used. Hydrophilic colloids, such as synthetic hydrophilic polymeric substances such as, can also be used.

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. The hardening agent can be added in an amount that can harden the photosensitive material to the extent that there is no need to add a hardening agent to the processing solution.
It is also possible to add a hardening agent to the processing solution.

For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5- ) Liacryloyl-hexahydro-3-triazine, 1.3
-vinylsulfonyl-2-propatol, etc.), ? 1-10 Ken compound (2,4-dichloro-6-hydroxy-
8-triazine tx, t)% muco10genic acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

A plasticizer can be added to the 710 silver gemide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the emulsion of the present invention for the purpose of increasing flexibility. A preferred plasticizer is RD17
It is a compound described in A of Karisho No. 643.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the emulsion of the present invention may contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability. can.

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
Compounds, image stabilizers, color capri inhibitors, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. Conventionally known methods for dispersing additives can be applied, and they are usually dissolved in a high-boiling organic solvent with a boiling point of about 150°C or higher, if necessary, in combination with a low-boiling point and/or water-soluble organic solvent, such as an aqueous gelatin solution. Stirrer, homogenizer, colloid mill, using surfactant in hydrophilic binder, 7
It may be emulsified and dispersed using a dispersing means such as O-ditooxer or an ultrasonic device, and then added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling point solvents include phenol visiting conductors that do not react with the oxidized form of the developing agent, phthalic acid alkyl esters, phosphoric esters, citric esters, benzoic esters, alkylamides, fatty acid esters, and trimedic acid esters with a boiling point of 150°C or higher. of organic solvents are used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of a light-sensitive material using the emulsion of the present invention, causing color turbidity or sharpness. A color anti-capri agent can be used to prevent deterioration in properties and noticeable graininess.

The color anti-capri agent may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

An image stabilizer that prevents deterioration of dye images can be used in the light-sensitive material using the emulsion of the present invention. Compounds that can be preferably used are those described in Section 2 J of RD17643.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good.

When dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer of a photographic material using the emulsion of the present invention, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change developability, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the emulsion of the present invention. Compounds that can be preferably used as development accelerators are those described in RD 17643, Section XXI, B-D, and development retardants include xxI of RD 17643q.
It is a compound listed in Section E. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The emulsion layer of a photosensitive material using the emulsion of the present invention has increased sensitivity,
For the purpose of increasing contrast or accelerating development, it may contain polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomol hepta-olins, quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, and the like.

In the light-sensitive material using the emulsion of the present invention, a fluorescent whitening agent can be used for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds that can be preferably used as optical brighteners are described in Section 7 of No. D17643.

A light-sensitive material using the emulsion of the present invention can be provided with auxiliary layers such as a filter layer, a halide etchant prevention layer, and an irradiation prevention layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process. Such dyes include oxonol dyes, hemioxonol dyes, steryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

A matting agent is added to the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the emulsion of the present invention for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking to each other. can be added. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resin, polycarbonate, and styrene. and copolymers thereof. The particle size of the matting agent is 0.
05μ to 10μ is preferable. The amount to add is 1 to 3
00117/rr? is preferred.

A lubricant can be added to the light-sensitive material using the emulsion of the present invention in order to reduce sliding friction.

An antistatic agent for the purpose of preventing static electricity can be added to a photographic material using the emulsion of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the emulsion layer and/or the mining colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the support. May be used for. Preferably used antistatic agents are the compounds described in RD 17643 Xl [.

The photographic emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the emulsion of the present invention has properties such as improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and photographic properties (promoting development,
Various surfactants can be used for the purpose of improving (hardening, sensitization, etc.).

The support used in the light-sensitive material using the emulsion of the present invention includes a flammable reflective support such as paper laminated with an α-olefin polymer (for example, polyethylene, polypropylene, ethylene/butene copolymer), or synthetic paper. , cellulose acetate, cellulose nitrate.

Examples include films made of semi-synthetic or synthetic polymers such as polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, flexible supports prepared by providing reflective layers on these films, glass, metals, ceramics, and the like.

The light-sensitive material using the emulsion of the present invention is prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
1 directly or for improving the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, anti-slip properties, friction properties, and/or other properties of the support surface; It may be applied through more than one subbing layer.

When coating a photosensitive material using the emulsion of the present invention, a thickener may be used to improve coating properties.

Also, for things like hardeners, which have quick reactivity and will cause gelation if added to the coating solution before coating, it is recommended to mix them using a static mixer or the like just before coating. preferable.

Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

Examples of the surfactant include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide type, glycerin type, and cricidol type, higher alkylamines, quaternary ammonium salts, pyridine, and others. Cationic surfactants such as heterocycles, phosphoniums or sulfoniums, carboxylic acids, sulfonic acids,
Anionic surfactants containing acidic groups such as phosphoric acid, sulfuric acid esters, and phosphoric acid esters; amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphoric acid esters of amino alcohols may be added.

Moreover, it is also possible to use a fluorine-based surfactant for the same purpose.

The emulsion of the present invention may also be applied to light-sensitive materials used in systems for obtaining high-contrast negative images with stable developers by using the hydrazine derivative described in U.S. Pat. No. 4,224,401. I'll come.

Any known developing method may be applied to the photosensitive material of the present invention. Developing agents used in the developer include dihydroxybenzene-based developing agents, 1-phenyl-3-pyrazolidone-based developing agents, p-aminophenol-based developing agents, etc. -pyrazolidones and dihydroxybenzenes or p-aminephenols and dihydroxybenzenes). Further, the light-sensitive material of the present invention may be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl bisulfite and hydroquinone.

In the above, examples of the dihydroxybenzene-based developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2.
Examples include 3-cycloba()'C2 quinone, 2,5-dimethylhydroquinone, etc., and l-phenyl-3-pyrazolidone-based developing crude drugs include 1-phenyl-3-pyrazolidone and 4,4-dimethyl-1-phenyl-3. -pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 4,4-dihydroxymethyl-1
-Phenyl-3-pyrazolidone, etc., p-aminophenol developing agents include p-aminophenol,
N-methyl-p-7 minophenol and the like are used.

A compound that provides free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, is added to the developer as a preservative. In the case of an infectious developer, sodium formaldehyde bisulfite, which does not give much free sulfite ions in the developer, may be used.

As the alkaline agent for the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, jetanolamine, triethanolamine, etc. are used. The pH of the developer is usually set to 9 or higher, preferably 9.7 or higher.

The developer solution may also contain organic compounds known as anticapri agents or development inhibitors. Examples include azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, metsushibutobenzimidazoles, mercaptothiadiazoles. , aminotriazoles, benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1*
3 + 3 a r 7 ) tetrazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid,
Benzene sulfinic acid, benzene sulfonic acid amide,
Examples include sodium 2-mercaptobenzimidazole-5-sulfonate.

The developer that can be used in the present invention may contain the same type of polyalkylene oxide as described above as a development inhibitor. For example, polyethylene oxide having a molecular weight of 1,000 to 10,000 can be incorporated in a range of 0.1 to 10 f/l.

It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetic acid, triethylenetetraamine hexaacetic acid, diethylenetetraamine pentaacetic acid, etc. as a water softener to the developer that can be used in the present invention.

As the fixer, one having a commonly used composition can be used.

As the fixing agent, in addition to thiosulfate and t-ocyanate, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The fixer can also contain a complex of ethylenediaminetetraacetic acid and trivalent iron ions as a sulfurizing agent.

Processing temperature and processing time are set appropriately, but usually 18℃~5
A processing temperature of 0 DEG C. is suitable, while rapid processing of 15 to 120 seconds using a so-called automatic processor is preferred.

(E) Examples Examples will be shown below to further specifically explain the present invention, but the present invention is not limited thereto and can be applied in various ways within the scope of the claims.

Example 1 Con) By the red double jet method! ! The silver chlorobromide (silver bromide 30 molt) emulsion with a variation coefficient of 11% prepared in No. 1 was subjected to second ripening by the sulfur-gold sensitization method under optimal conditions to achieve the highest sensitivity and lowest fog, and then the following After adding the sensitizing dye and the mercaptotetrazole compound (additives) under the conditions shown in Table 1 of It was applied at an amount of 4.1 f/d.

Additives - people A protective layer was applied on the sample obtained by grinding.

A silver chloride-based emulsion is used for rapid processing in a range of 10 to 20 seconds, but in order to improve the drying properties of automatic processors, the total amount of gelatin used in the silver halide emulsion layer and the protective layer is 4.2 f. /lr? Closed.

The sample thus obtained was exposed to helium-neon laser light and treated with the following treatment solution.

Developer solution> Potassium hydroxide 17f Sodium sulfite 60r Diethylenetriaminepentaacetic acid 2 and Potassium carbonate
52 boric acid
32 Hydroquinone 5f Diethylene glycol 2F! ! 1 5-methylbenzotriazole 0.62 acetic acid
1.82 potassium bromide
2 to IL with water (pH 10,
(adjust to 15).

Fixer> Ammonium thiosulfate 140 f Sodium sulfite 15 f Ethylene diamine acetate red disodium dihydrate 25 ■ Sodium hydroxide 6 is made up to 1 t with water (adjust to pH 4.95 with acetic acid).

The development time was 15 seconds, and the dry period from development to completion of drying was
The time to dry was set to 60 seconds. The results obtained are shown in Table 1.

Example 2 After adding field dye and tetrazaindene compound (Additive-B) to an emulsion subjected to second ripening in the same manner as in Example 1 under the conditions shown in Table 2 below, an activator was added. A silver amount of 4.1 t/n? was coated on a polyethylene terephthalate support by adding a coating aid and a hardening agent such as It was applied so that

Additive-B The sample thus obtained was treated in the same manner as in Example-1.

Table 2 Note) Phase correspondence variation C when sensitivity 'i of sample 2 is set to 100
F) Effects of the Invention According to the present invention, a silver halide photographic material can be obtained which is highly sensitive to helium-neon laser light and has good dye removal during rapid processing.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having a silver halide emulsion layer on a support, the silver halide contained in the silver halide emulsion layer contains 50 mol% or more of silver chloride. Silver chlorobromide or silver chloroiodobromide, and the following (a)
A silver halide photographic material that satisfies the conditions of ~(c). (a) Silver halide grains contained in the above silver halide photographic material are substituted with iodine atoms in an amount corresponding to a molar ratio of 0.1 to 1.0%. (b) The above silver halide emulsion has the following general formula [I]
, [II] and [III], supersensitized with at least two types of sensitizing dyes. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.▼ (Here, R_1 represents an alkyl group, R_2 represents a sulfoalkyl group or sulfoaralkyl group, and R_3 represents a lower alkyl group. W_1 and W_2 represent an alkylene group. )
General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. or hydroxyl group.) General formula [I
II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R_7 represents an alkyl group, R_8 represents a sulfoalkyl group, sulfoaralkyl group, R_9 represents a lower alkyl group, W_7 and W_8 represent an alkyl group, an alkoxy group,
Represents a hydroxy group. (c) A silver halide photographic emulsion in which at least one of a mercaptotetrazole compound or a tetrazaindene compound is added in an amount of 10^-^4 to 10^-^2 moles relative to silver in the silver halide emulsion. .